Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization and method for producing polyolefin

ABSTRACT

A magnesium compound obtained by reacting metallic magnesium having a sphericity (S) of less than 4.00, the sphericity (S) being represented by the following formula (I), an alcohol, and a halogen and/or a halogen-containing compound containing halogen atoms in an amount of 0.0001 gram atom or more relative to one gram atom of the metallic magnesium,
 
 S =( L   1   /L   2 ) 3   (I)
         wherein L 1  represents the maximum diameter of projection views of metallic magnesium determined by photographing with a scanning electron microscope and thereafter an image processing, and L 2  represents a diameter of a circle having an area equal to the area of the projection view of metallic magnesium. A solid catalyst component is obtained from the magnesium compound and a titanium compound, and a catalyst for olefin polymerization is obtained using the solid catalyst component.

TECHNICAL FIELD

The invention relates to a magnesium compound, a solid catalystcomponent for olefin polymerization, a catalyst for olefinpolymerization and a method for producing a polyolefin.

TECHNICAL BACKGROUND

Hitherto, magnesium compounds such as magnesium chloride and magnesiumalkoxides have been widely used as a support material without beingmilled in the field of catalysts for olefin polymerization, specificallythe monopolymerization or copolymerization of olefins such as ethyleneand propylene. This may improve the catalyst activity and the morphologyof polyolefin powder.

For example, for improving an olefin polymer in the morphology includinga particle size, form, etc., JP-A-S63-280707 discloses a method in whicha magnesium compound is supported on an inorganic oxide such as silica,or JP-A-S58-000811 discloses a method in which a magnesium compound isonce dissolved in a solvent such as an alcohol and then precipitateagain, which precipitate is used.

However, these methods include very complicated steps, since theyrequire the procedures of supporting, dissolving and precipitating amagnesium compound. Further, these methods have a defect that thecatalyst is poor in stability of performance since the catalyticactivity is high only at an early stage of the polymerization.

JP-A-H4-130107 discloses to use as a support of catalysts a magnesiumcompound obtained by reacting metallic magnesium, an alcohol and acertain amount of halogen. However, the sphericity or particle sizedistribution of support and polymer powder obtained may not besatisfactory dependently on the particulate properties of metallicmagnesium or conditions under which a magnesium compound is produced.

In view of the foregoing the invention has been made and an objectthereof is to provide a magnesium compound, a solid catalyst componentfor olefin polymerization, a catalyst for olefin polymerization and amethod for producing a polyolefin, which can give a polyolefin with anarrow particle size distribution and/or a nearly spherical form withoutreducing stereoregularity and catalyst properties such as polymerizationactivity.

The inventors made efforts to find that the above subject can be solvedby producing a solid catalyst component for olefin polymerization byreacting a magnesium compound and a titanium compound, the magnesiumcompound being obtained from metallic magnesium with a specifiedsphericity or particle size distribution index, or merallic magnesiumwith an oxidized coating film having a specified thickness; or obtainedby reacting metallic magnesium with a specified average particle size, aspecified amount of an alcohol and a halogen and/or a halogen-containingcompound under specified stirring conditions. The invention has beencompleted by the finding.

DISCLOSURE OF THE INVENTION

The invention provides the following magnesium compound and the like.

[1] A magnesium compound obtained by reacting

metallic magnesium having a sphericity (S) of less than 4.00, thesphericity (S) being represented by the following formula (I),

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,S=(L ₁ /L ₂)³  (I)

wherein L₁ represents the maximum diameter of projection views ofmetallic magnesium determined by photographing with a scanning electronmicroscope and thereafter an image processing, and L₂ represents adiameter of a circle having an area equal to the area of the projectionview of metallic magnesium.

[2] A magnesium compound obtained by reacting

metallic magnesium having a particle size distribution index (P) of lessthan 4.0, the index (P) being represented by the following formula (II),

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,P=(D ₉₀ /D ₁₀)  (II)

wherein D₉₀ represents a particle size of the metallic magnesiumcorresponding to 90% of cumulative weight percentage, and D₁₀ representsa particle size of the metallic magnesium corresponding to 10% ofcumulative weight percentage.

[3] A magnesium compound obtained by reacting with stirring

metallic magnesium, an average particle size (D₅₀) corresponding to 50%of cumulative weight percentage of the metallic magnesium being from 50to 2,000 μm,

an alcohol at a molar ratio relative to one mol of the metallicmagnesium (ROH/Mg) of from 4 to 40, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,

in a stirring vessel with a stirring axis provided with a stirring bladehaving a blade diameter d(m) at a speed of rotation n (number ofrevolution per minute) under conditions of n³d² being from 4.3×10³ to4.0×10⁶.

[4] A magnesium Compound Obtained by Reacting

metallic magnesium having an oxidized coating film with a thickness of 1μm or less,

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium.

[5] The magnesium compound according to any one of [1] to [4], whereinthe halogen is iodine.

[6] The magnesium compound according to any one of [1] to [5], whereinthe halogen-containing compound is magnesium chloride.

[7] The magnesium compound according to any one of [1] to [6], whereinthe temperature of the reaction of the metallic magnesium, the alcoholand the halogen and/or the halogen-containing compound is from 30 to 90°C.

[8] The magnesium compound according to [1], which has a sphericity (S′)of less than 1.30, the sphericity (S′) being represented by thefollowing formula (III),S′=(L ₃ /L ₄)³  (III)

wherein L₃ represents the maximum diameter of projection views of themagnesium compound determined by photographing with a scanning electronmicroscope and thereafter an image processing, and L₄ represents adiameter of a circle having an area equal to the area of the projectionview of magnesium compound.

[9] The magnesium compound according to [2] or [4], which has a particlesize distribution index (P′) of less than 3.4, the index (P′) beingrepresented by the following formula (IV),P′=(D ₉₀ /D ₁₀)  (IV)

wherein D₉₀ represents a particle size of the magnesium compoundcorresponding to 90% of cumulative weight percentage, and D₁₀ representsa particle size of the magnesium compound corresponding to 10% ofcumulative weight percentage.

[10] The magnesium compound according to [3], which has a particle sizedistribution index (P′) of less than 3.4, the index (P′) beingrepresented by the formula (IV), and has a sphericity (S′) of less than1.30, the sphericity (S′) being represented by the formula (III).[11] The magnesium compound according to [4], which is metallicmagnesium formed into particles in an atmosphere of an inert gas with anaverage diameter of 1 cm or less.[12] A solid catalyst component for olefin polymerization, which isobtained by reacting

(a) the magnesium compound according to any one of [1] to [11] and

(b) a titanium compound.

[13] The solid catalyst component for olefin polymerization according to[12], which is obtained by reacting further (c) a halogenated compoundand/or (d) an electron donating compound with the compounds (a) and (b).

[14] The solid catalyst component for olefin polymerization according to[13], wherein the hologenated compound (c) is silicon tetrachloride.

[15] A catalyst for olefin polymerization comprizing the followingcompounds [A] and [B], or the following compounds [A], [B] and [C]:

[A] the solid catalyst component for olefin polymerization according toany one of [12] to [14];

[B] an organic aluminum compound;

[C] an electron donating compound.

[16] A method for producing a polyolefin using the catalyst for olefinpolymerization according to [15].

[17] A method for producing a magnesium compound, comprising reacting

metallic magnesium having a sphericity (S) of less than 4.00, thesphericity (S) being represented by the following formula (I),

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,S=(L ₁ /L ₂)³  (I)

wherein L₁ represents the maximum diameter of projection views ofmetallic magnesium determined by photographing with a scanning electronmicroscope and thereafter an image processing, and L₂ represents adiameter of a circle having an area equal to the area of the projectionview of metallic magnesium.

[18] A method for producing a magnesium compound, comprising reacting

metallic magnesium having a particle size distribution index (P) of lessthan 4.0, the index (P) being represented by the following formula (II),

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,P=(D ₉₀ /D ₁₀)  (II)

wherein D₉₀ represents a particle size of the metallic magnesiumcorresponding to 90% of cumulative weight percentage, and D₁₀ representsa particle size of the metallic magnesium corresponding to 10% ofcumulative weight percentage.

[19] A method for producing a magnesium compound, comprising reactingwith stirring

metallic magnesium, an average particle size (D₅₀) corresponding to 50%of cumulative weight percentage of the metallic magnesium being from 50to 2,000 μm,

an alcohol at a molar ratio relative to one mol of the metallicmagnesium (ROH/Mg) of from 4 to 40, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium,

in a stirring vessel with a stirring axis provided with a stirring bladehaving a blade diameter d(m) at a speed of rotation n (number ofrevolution per minute) under conditions of n³d² being from 4.3×10³ to4.0×10⁶.

[20] A method for producing a magnesium compound, comprising reacting

metallic magnesium having an oxidized coating film with a thickness of 1μm or less,

an alcohol, and

a halogen and/or a halogen-containing compound containing halogen atomsin an amount of 0.0001 gram atom or more relative to one gram atom ofthe metallic magnesium.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic drawing showing the catalyst for olefinpolymerization, and a process for producing an olefin polymer, providedby the invention.

FIG. 2 is a schematic drawing showing another catalyst for olefinpolymerization, and a process for producing an olefin polymer, providedby the invention.

FIG. 3 is a schematic drawing showing still another catalyst for olefinpolymerization, and a process for producing an olefin polymer, providedby the invention.

FIG. 4 is a schematic drawing showing yet another catalyst for olefinpolymerization, and a process for producing an olefin polymer, providedby the invention.

PREFERRED EMBODIMENTS OF THE INVENTION

Catalyst components and the like used in the invention will be explainedhereinafter. The embodiments shown hereinafter are preferredembodiments, and the invention is not limited thereto.

1. Catalyst Components

[A1] Solid Catalyst Component for Olefin Polymerization

(a1) Magnesium Compound

In view of the form of polymer particles and polymerization activity,the invention uses, as a magnesium compound (a1), a compound that isobtained by reacting metallic magnesium having a sphericity (S) of lessthan 4.00, preferably less than 2.50, an alcohol, and a halogen and/or ahalogen-containing compound containing halogen atoms in an amount of0.0001 gram atom or more relative to one gram atom of the metallicmagnesium. The sphericity (S) is represented by the following formula(I),S=(L ₁ /L ₂)³  (I)

wherein L₁ represents the maximum diameter of projection views ofmetallic magnesium determined by photographing with a scanning electronmicroscope and thereafter an image processing, and L₂ represents adiameter of a circle having an area equal to the area of the projectionview of metallic magnesium.

The form of polymer particles are degraded and polymerization activityalso decrease, if the sphericity (S) of metallic magnesium is 4.00 ormore. We think that this is caused by that the use of metallic magnesiumwith a low sphericity leads to the generation of large particles ofsolid catalyst component with a lower polymerization activity.

The sphericity (S) shows the degree of spherical form of a substance.The substance with sphericity=1 means a complete sphere. Metallicmagnesium particles each are closer to a complete sphere as S is closerto 1.

Such metallic magnesium with a sphericity of less than 4.00 can beproduced by the combination of cutting with a lathe, a file or the likeand milling with a ball mill or the like, or an atomization method(melting/spray method).

The alcohol is preferably selected from lower alcohols having 1 to 6carbon atoms. Ethanol is particularly preferred, since ethanol serves togive a solid product that remarkably improves the exhibition ofcatalytic performances of polymerization activity and the like. Whilethe purity and water content of the alcohol are not critical, either.When an alcohol having a large water content is used, however, a coatingfilm of magnesium hydroxide is formed on the metal magnesium surface, sothat it is preferred to use an alcohol having a water content of 1% orless, and it is particularly preferred to use an alcohol having a watercontent of 2,000 ppm or less. Further, for obtaining an olefin polymerhaving better particle properties (individual particle shape andparticle size distribution, hereinafter referred to as morphology insome cases), a smaller water content is preferred, and the water contentis generally desirably 200 ppm or less.

The halogen is selected from chlorine, bromine or iodine, and iodine isparticularly suitably used.

Further, the halogen atom of the halogen-containing compound ispreferably chlorine, bromine or iodine. The halogen-containing compoundis particularly preferably a halogen-containing metal compound.Specifically, the halogen-containing compound can be preferably selectedfrom MgCl₂, MgI₂, Mg(OEt)Cl, Mg(OEt)I, MgBr₂, CaCl₂, NaCl or KBr etc. Ofthese, MgCl₂ is particularly preferred. The state, form and particlesize of these compounds are not limited, and a compound being in anystate and having any form and any particle size can be used. Forexample, a solution of such a compound in an alcohol solvent (e.g.,ethanol) can be used.

It appears that Iodine or MgCl₂ is preferred, since the effect whichimproves the solubility of the magnesium compound to ethanol is high.

The amount of the alcohol per mole of the metal magnesium is preferably2 to 100 mol, particularly preferably 5 to 50 mol. When the amount ofthe alcohol is too large, the yield of the magnesium compound (a1)having excellent morphology may decrease. When it is too small, stirringin a reaction vessel may not smoothly proceed, while the molar ratio isnot limited thereto.

When the halogen or the halogen-containing compound is used, the amountof the halogen atoms in the halogen or the halogen-containing compoundper gram atom of the metal magnesium is 0.0001 gram atom or more,preferably 0.0005 gram atom or more, more preferably 0.001 gram atom ormore. When the amount of the halogen is less than 0.0001 gram atom, andwhen the magnesium compound (a1) is used as a support of a solidcatalyst component, the catalyst may be poor in polymerization activityor an olefin polymer may be defective in morphology, and the like.

In the invention, the halogens and the halogen-containing compounds maybe used solely each, and two or more halogens or halogen-containingcompounds of these may be used in combination. Further, the halogen andthe halogen-containing compound may be used in combination. When thehalogen and the halogen-containing compound are used in combination, theamount of total halogen atoms in the halogen and the halogen-containingcompound per gram atom of the metal magnesium is 0.0001 gram atom ormore, preferably 0.0005 gram atom or more, more preferably 0.001 gramatom or more.

While the upper limit of the amount(s) of the halogen and/or thehalogen-containing compound is not specially limited, the upper limitmay be set as required so long as the magnesium compound (a1) for use inthe invention can be obtained. Generally, the above upper limit ispreferably less than 0.06 gram atom.

In the process for the production of the magnesium compound (a1),provided by the invention, the amount of the halogen and/or thehalogen-containing compound is determined as required, whereby theparticle size of the magnesium compound (a1) can be controlled asrequired.

The magnesium compound (a1) is usually prepared by reacting the metallicmagnesium having the above sphericity (S), the alcohol and the halogenand/or the halogen-containing compound until the generation of hydrogengas is no longer observed (generally, for 1 to 30 hours). Specifically,when iodine is used as a halogen, the magnesium compound (a1) can beprepared by a method in which iodine in the form of a solid is chargedinto the metal magnesium and the alcohol and then the mixture is allowedto react under heat, a method in which a solution of iodine in analcohol is added dropwise to the metal magnesium and the alcohol and themixture is allowed to react under heat, or a method in which, while themetal magnesium and an alcohol solution are heated, a solution of iodinein an alcohol is added dropwise to allow the mixture to react.

Each method is preferably carried out in the atmosphere of an inert gas(e.g., nitrogen gas or argon gas) and optionally in the presence of aninert organic solvent (e.g., saturated hydrocarbon such as n-hexane).

The metallic magnesium, the alcohol and the halogen and/or thehalogen-containing compound are usually allowed to react at thetemperature of 30 to 90° C., preferably at 30 to 60° C. The performanceimproves in the range thereof. It appears that the uniform magnesiumcompound can be produced since a balance between the rate of reactionand the solubility is excellent.

Further, it is not required to charge the entire amount of each of themetal magnesium, the alcohol and the halogen and/or thehalogen-containing compound at once from the beginning, and they may bedivided and partially charged. For example, the alcohol is entirelycharged in the beginning, the metal magnesium is divided into severalportions and such portions are charged separately. In this embodiment,the momentary generation of a large amount of hydrogen gas can beprevented, which is desirable in view of safety. Further, the size of areaction vessel can be decreased. Further, it is also made possible toprevent the dissipation of alcohol, halogen and the like caused by themomentary generation of a large amount of hydrogen gas. While the numberof the divisional portions can be determined by taking account of thesize of the reaction vessel and is not specially limited, suitably, eachis generally divided into five to ten portions in view ofcomplicatedness of procedures.

Further, the reaction may be carried out by any one of a batch methodand a continuous method. Furthermore, there may be employed a variantmethod in which the entire amount of the alcohol is charged in thebeginning, a small amount of the metal magnesium is added to thealcohol, a product formed by a reaction is removed by separating it intoother vessel, then, a small amount of the metal magnesium is charged,and these procedures are repeated.

When the magnesium compound (a1) thus obtained is used for thepreparation of the solid catalyst component [A1], a dry product may beused, or a product obtained by filtering and then washing with an inertsolvent such as heptane may be used.

In any case, the magnesium compound (a1) that is obtained in theinvention can be used as a support of the solid catalyst component,without any pulverization or any sieving procedure for attaining auniform particle size distribution. The magnesium compound (a1) isnearly spherical and has a sharp particle size distribution.Furthermore, the variation in sphericity of particles of the magnesiumcompound (a1) is small.

The magnesium compound (a1) generally has a sphericity (S′) of less than1.30, preferably less than 1.28. The sphericity (S′) is represented bythe following formula (III),S′=(L ₃ /L ₄)³  (III)

wherein L₃ represents the maximum diameter of projection views of themagnesium compound determined by photographing with a scanning electronmicroscope and thereafter an image processing, and L₄ represents adiameter of a circle having an area equal to the area of the projectionview of magnesium compound.

The magnesium compound (a1) with such a sphericity (S′) is preferred inthe view of catalyst activity and form of polymer particles.

Particles of magnesium compound (a1) each are closer to a completesphere as S′ is closer to 1, like the sphericity (S) of metallicmagnesium.

The magnesium compound (a1) generally has a particle size distributionindex (P′) of less than 4.0, preferably less than 3.8. The index (P′) isrepresented by the following formula (IV),P′=(D ₉₀ /D ₁₀)  (IV)

wherein D₉₀ represents a particle size of the metallic magnesium (a1)corresponding to 90% of cumulative weight percentage, and D₁₀ representsa particle size of the metallic magnesium (a1) corresponding to 10% ofcumulative weight percentage.

The use of the magnesium compound (a1) with such a particle sizedistribution index (P′) enables to enhance polymerization activity andimprove the form of polymer particles.

The particle size distribution index (P′) shows the width of particlesize distribution of magnesium compound (a1). A smaller value thereofmeans that the particle size distribution is narrow or sharp, or thatmany particles of magnesium compound (a1) with a uniform diameter arecontained.

The magnesium compound (a1) with such a sphericity (S′) of less than1.30 and a particle size distribution index (P′) of less than 4.0 can beproduced by using metallic magnesium with the above-mentioned sphericity(S).

The magnesium compounds (a1) may be used solely, or two or more thereofmay be used in combination.

Such magnesium compounds (a1) are solid, and substantially made ofmagnesium alkoxides practically.

Specific examples of the magnesium alkoxides include dialkoxymagnesiumcompounds such as dimethoxymagnesium, diethoxymagnesium,dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium,dioctoxymagnesium, diphenoxymagnesium and dicyclohexyloxymagnesium,diallyloxymagnesium; alkoxyalkylmagnesium compounds such asethoxyethylmagnesium, phenoxymethylmagnesium, ethoxyphenylmagnesium,cyclohexyloxyphenylmagnesium, allyloxyalkylmagnesiu,alkoxyallylmagnesium, allyloxyallylmagnesium; alkoxymagnesium halidessuch as butoxymagnesium chloride, cyclohexyloxymagnesium chloride,phenoxymagnesium chloride, ethoxymagnesium chloride, ethoxymagnesiumbromide, butoxymagnesium bromide and ethoxymagnesium iodide, andallyloxymagnesium halides. Of these alkoxy-group-containing magnesiumcompounds, dialkoxymagnesium compounds are preferred, anddiethoxymagnesium is particularly preferred, in view of polymerizationactivity and stereoregularity.

(b1) Titanium Compound

In view of polymerization activity and the like, the titanium compoundcan be preferably selected from compounds represented by the followinggeneral formula (V),TiX_(n)(OR)_(4-n)  (V)

wherein X represents a halogen atom, and R is a hydrocarbon group having1 to 10 carbon number. One of these may be the same as, or differentfrom, the other or every other one. N is an integer of 0 to 4.

In the above general formula (V), the halogen atom X is preferably achlorine or bromine atom, particularly preferably a chlorine atom. Thehydrocarbon group R is preferably an alkyl group, an alkenyl group, acycloalkenyl group, an aryl group or an aralkyl group and the like, andparticularly preferably an linear or branched alkyl group. Further, Rmay be a saturated or an unsaturated group. It may be a linear orbranched, or it may be cyclic, and it may contain a hetero element suchas sulfur, nitrogen, oxygen, silicon or phosphorus. Specific examples ofR include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl, butenyl,cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl andphenethyl and the like. And, n is perferably 4.

Specific examples of the titanium compounds (b1) of the above generalformula (V) include tetraalkoxytitanium such as tetramethoxytitanium,tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium,tetra-n-butoxytitanium, tetraisobutoxytitanium,tetracyclohexyloxytitanium and tetraphenoxytitanium; titaniumtetrahalides such as titanium tetrachloride, titanium tetrabromide andtitanium tetraiodide; alkoxytitanium trihalides such as methoxytitaniumtrichloride, ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride and ethoxytitanium tribromide;dialkoxytitanium dihalides such as dimethoxytitanium dichloride,diethoxytitanium dichloride, diisopropoxytitanium dichloride,di-n-propoxytitanium dichloride and diethoxytitanium dibromide; andtrialkoxytitanium monohalides such as trimethoxytitanium chloride,triethoxytitanium chloride, triisopropoxytitanium chloride,tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride. Ofthese, high-halogenated titanium compounds are preferred, and titaniumtetrachloride is particularly preferred, in view of polymerizationactivity. These titanium compounds (b1) may be used solely, or two ormore thereof may be used in combination.

(c1) Halogenated Compound

If necessary, a halogenated compound (c1) is employed in a solidcatalyst component for olefin polymerization. The halogenated compound(c1) is preferably used since it may improve the particulate form of anolefin polymer and make particle size distribution narrower. Halogenatedcompounds (c1) include halogens such as iodine, bromine, chlorine andfluorine; hydrogen halides such as hydrogen iodide, hydrogen bromide,hydrogen chloride and hydrogen fluoride; silicon tetrachloride andsilicon tetrabromide; silicon halides such as trichlorosilane,dichlorosilane and monochlorosilane; carbon halides such as carbontetrachloride and hexacholoroethane; halogen-substituted alcohols suchas 2,2,2-trichloroethanol; halogen-substituted phenols such asp-chlorophenol; boron halides such as boron trichloride; aluminumhalides such as aluminum trichloride; and tin halides such as tintetrachloride. Of these, silicon tetrachloride is preferred in view ofcontrolling the particle size of a polymer. These halogenated compounds(c1) may be used solely, or two or more thereof may be used incombination.

(d1) Electron-donating Compound

If necessary, an electron-donating compound (d1) is employed in a solidcatalyst component for olefin polymerization. The electron-donatingcompound (d1) is preferably used since it may improve thestereoregularity of an olefin polymer. The electron-donating compounds(d1) include oxygen-containing compounds such as alcohols, phenols,ketones, aldehydes, carboxylic acids, malonic acid, esters of organicacids or inorganic acids and ethers such as monoether, diether andpolyether, and nitrogen-containing compounds such as ammonia, amine,nitrile and isocyanate. Of these, esters of polyhydric carboxylic acidsare preferred, and esters of aromatic polyhydric carboxylic acids aremore preferred. Of these, a monoester and/or a diester of aromaticdicarboxylic acid are/is particularly preferred in view ofpolymerization activity. Further, the organic groups of the esterportions are preferably a linear, branched or cyclic aliphatichydrocarbon group.

Specific examples of the electron-donating compounds include dialkylesters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-hexyl, cyclohexyl,n-heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl,2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl,3-methylpentyl, 2-ethylpentyl or 3-ethylpentyl dicarboxylates such asphthalate, naphthalene-1,2-dicarboxylate, naphthalene-2,3-dicarboxylate,5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylate,5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate, indan-4,5-dicarboxylateand indan-5,6-dicarboxylate. Of these, phthalic acid diesters arepreferred, and phthalic acid diesters in which the organic group of anester portion is a linear or branched aliphatic hydrocarbon group having4 or more carbon atoms are particularly preferred. Preferable specificexamples thereof include di-n-butyl phthalate, diisobutyl phthalate,di-n-heptyl phthalate and diethyl phthalate and the like. Theseelectron-donating compounds (d1) may be used solely, or two or morethereof may be used in combination.

[A2] Solid Catalyst Component for Olefin Polymerization

(a2) Magnesium Compound

In view of improving the form or morphology of polymer powder andpolymerization activity, the invention uses, as a magnesium compound(a2), a compound that is obtained by reacting metallic magnesium havinga particle size distribution index (P) of less than 4.0, preferably lessthan 3.0, an alcohol, and a halogen and/or a halogen-containing compoundcontaining halogen atoms in an amount of 0.0001 gram atom or morerelative to one gram atom of the metallic magnesium. The index (P) isrepresented by the following formula (II),P=(D ₉₀ /D ₁₀)  (II)

wherein D₉₀ represents a particle size of the metallic magnesiumcorresponding to 90% of cumulative weight percentage, and D₁₀ representsa particle size of the metallic magnesium corresponding to 10% ofcumulative weight percentage.

The metallic magnesium with an index (P) of 4.0 or more is not preferredsince a solid catalyst component with a high catalyst activity cannot beobtained from a magnesium compound prepared by reacting it.

Such metallic magnesium (a2) with a particle size distribution index ofless than 4.0 can be produced by preparing particles by cutting,mechanically milling or melting/spray, and then sieving them with meshesand so on.

The metallic magnesium is not critical with regard to its form and thelike so far as it has the above particle size distribution index.Therefore metallic magnesium having any particle form, for example,metallic magnesium having a granular, ribbon-shaped or powdery form, maybe used.

The average particle size D₅₀ corresponding to 50% of cumulative weightpercentage of the metallic magnesium is preferably 10 to 10,000 μm, morepreferably 50 to 2,000 μm. If the average particle size is smaller, itsreaction may proceed with violence and difficult to be controlled. Ifthe particle size is too large, its reaction time may be long with a lowproducibility. If it is out of the range, the morphology such asparticle size distribution and sphericity of a magnesium compoundobtained may be degraded.

An alcohol, a halogen and a halogen-containing compound are the same asthose explained in the magnesium compound (a1) and their explanation isthus omitted.

In order to produce the magnesium compound (a2), metallic magnesium withthe above particle size distribution index (P), alcohol, and halogenand/or halogen-containing compound are generally reacted in the samemanner as in the magnesium compound (a1).

The magnesium compound (a2) of the invention can be used as a supportfor a solid catalyst component without operations such as milling orclassification for a narrow particle size distribution like themagnesium compound (a1). The magnesium compound (a2) is nearly sphericaland has a sharp particle size distribution. The particles thereof have asmall variability of sphericity.

The magnesium compound (a2) generally has a particle size distributionindex (P′) represented by the above formula (IV) of less than 3.4,preferably less than 3.2.

By using a magnesium compound (a2) with such a particle sizedistribution index (P′), the polymerization activity is enhanced and apolymer with more excellent particle morphology can be obtained.

The magnesium compound (a2) generally has a sphericity (S′) representedby the above formula (III) of less than 2.00, preferably less than 1.50.

The magnesium compound (a2) with such a sphericity (S′) is preferred inview of catalyst activity and morphology of polymer particles.

Such a magnesium compound (a2) with a particle size distribution index(P′) of less than 3.4 and a sphericity (S′) of less than 2.00 can beproduced by using metallic magnesium with the above particle sizedistribution index (P).

The magnesium compound (a2) may be used solely or two or more thereofprepared by different methods may be used in combination.

Such a magnesium compound (a2) is solid and substantially made of amagnesium alkoxide. Examples of the magnesium alkoxide are the same asthose of the magnesium compound (a1).

(b2) Titanium Compound

The titanium compound (b2) is as explained with regard to the titaniumcompound (b1) for use in the solid catalyst component [A1], so that itsexplanation is omitted.

(c2) Halogenated Compound

The halogenated compound (c2) is as explained with regard to thetitanium compound (c1) for use in the solid catalyst component [A1], sothat its explanation is omitted.

(d2) Electron-donating Compound

The electron-donating compound (d2) is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

[A3] Solid Catalyst Component for Olefin Polymerization

(a3) Magnesium Compound

The invention uses, as a magnesium compound (a3), a compound that isobtained by reacting with stirring metallic magnesium, an averageparticle size (D₅₀) corresponding to 50% of cumulative weight percentageof the metallic magnesium being from 50 to 2,000 μm, an alcohol at amolar ratio relative to one mol of the metallic magnesium (ROH/Mg) offrom 4 to 40, and a halogen and/or a halogen-containing compoundcontaining halogen atoms in an amount of 0.0001 gram atom or morerelative to one gram atom of the metallic magnesium, in a stirringvessel with a stirring axis provided with a stirring blade having ablade diameter d(m) at a speed of rotation n (number of revolution perminute) under conditions of n³d² being from 4.3×10³ to 4.0×10⁶.

If D₅₀, ROH/Mg and n³d² are out of the above range, the particle sizedistribution of polymer powder obtained may be wider, its sphericity maydecrease or it may agglomerate.

We presume as to D₅₀ that the reason therefor is as follows. Particlesof magnesium compound consist of plate-like crystals. The particle sizeand form of a magnesium compound depend on the balance of a reactionspeed (promoting agglomeration of plate-like crystals), collisionbetween particles, collision between particles and a wall of instrumentor a shear from a fluid (suppressing agglomeration of crystals). Fromthis point of view, if the reaction occurs at the same time, moreuniform particles can be obtained. In the case of using particles with asmaller diameter, the reaction speed becomes higher due to the largespecific surface area but the amount of a coating film becomes larger.This may influence the uniformity of reaction. We presume as to ROH/Mgthat if the Mg concentration is too high, stirring may disadvantageouslybecome ununiform, and if the Mg concentration is too low, particles maydisadvantageously insufficiently collide with each other. We presume asto n³d² that if the mixture is weakly stirred, its flow may becomeuniform with an ununiform reaction, and if it is strongly stirred, itmay become difficult for the plate-like crystals of magnesium compoundto agglomerate as larger particles.

D₅₀ is preferably 75 to 1,800 μm, ROH/Mg is preferably 5 to 20, and n³d²is preferably 1.3×10⁴ to 8.4×10⁵.

Such metallic magnesium with an average particle size (D₅₀) of 50 to2,000 μm can be produced by a mechanically milling, cutting,melting/spray and so on.

A blade diameter d and rotary speed n are not limited and they can beproperly adjusted so far as n³d² meets the above requirement.

Any blades used for slurry mixing stirring such as a max blend blade,full-zone blade, paddle (flat) blade, inclined blade, turbine blade andanchor blade may be used as the stirring blade. They may be used inordinary form or multistage form. A plurality of baffles may be providedon the sidewall of a stirring vessel along the axial direction.

Of these blades, a max blend blade with baffles is preferred.

The metallic magnesium is not critical with regard to its form and thelike so far as it has the above average particle size (D₅₀). Thereforemetallic magnesium having any particle form, for example, metallicmagnesium having a granular, ribbon-shaped or powdery form, may be used.

An alcohol, a halogen and a halogen-containing compound are the same asthose explained in the magnesium compound (a1) except for theabove-explanation and their explanation is thus omitted.

In order to produce the magnesium compound (a3), metallic magnesium withthe above average particle size (D₅₀), alcohol with the above molarratio (ROH/Mg), and halogen and/or halogen-containing compound with theabove gram atomic ratio are reacted under the above stirring conditionslike the magnesium compound (a1).

The magnesium compound (a3) of the invention can be used as a supportfor a solid catalyst component without operations such as milling orclassification for a narrow particle distribution like the magnesiumcompound (a1). The magnesium compound (a3) is nearly spherical and has asharp particle size distribution. The particles thereof have a smallvariability of sphericity.

The magnesium compound (a3) generally has a particle size distributionindex (P′) represented by the above formula (IV) of less than 3.4,preferably less than 3.2.

By using a magnesium compound (a3) with such a particle sizedistribution index (P′), the polymerization activity is enhanced and apolymer with more excellent particle morphology can be obtained.

The magnesium compound (a3) generally has a sphericity (S′) representedby the above formula (III) of less than 1.30, preferably less than 1.28.

The magnesium compound (a3) with such a sphericity (S′) is preferred inview of catalyst activity and morphology of polymer particles.

Such a magnesium compound (a3) with a particle size distribution index(P′) of less than 3.4 and a sphericity (S′) of less than 1.30 can beproduced by reacting the above metallic magnesium, alcohol and halogenand/or halogen-containing compound under the above stirring conditions.

The magnesium compound (a3) may be used solely or two or more thereofprepared by different methods may be used in combination.

Such a magnesium compound (a3) is solid and substantially made of amagnesium alkoxide. Examples of the magnesium alkoxide are the same asthose of the magnesium compound (a1).

(b3) Titanium Compound

The titanium compound (b3) is as explained with regard to the titaniumcompound (b1) for use in the solid catalyst component [A1], so that itsexplanation is omitted.

(c3) Halogenated Compound

The halogenated compound (c3) is as explained with regard to thetitanium compound (c1) for use in the solid catalyst component [A1], sothat its explanation is omitted.

(d3) Electron-donating Compound

The electron-donating compound (d3) is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

[A4] Solid Catalyst Component for Olefin Polymerization

(a4) Magnesium Compound

In view of the form of polymer particles and polymerization activity,the invention uses, as a magnesium compound (a4), a compound that isobtained by reacting metallic magnesium having an oxidized coating filmwith a thickness of 1 μm or less, preferably 0.5 μm or less, morepreferably 0.1 μm or less, an alcohol, and a halogen and/or ahalogen-containing compound containing halogen atoms in an amount of0.0001 gram atom or more relative to one gram atom of the metallicmagnesium.

If metallic magnesium having an oxidized coating film with a thicknessmore than 1 μm is used, the particulate morphology of a magnesiumcompound (a4) or polyolefin obtained therefrom, or polymerizationactivity may be degraded.

Compounds constituting the oxidized coating film include Mg(OH)₂, MgO,MgCO₃, MgSO₄, double salts thereof and those containing crystal water.Examples of crystal-water-containing compounds include MgSO₄ 7H₂O.Examples of the double salts include (MgCO₃)₄ Mg(OH)₂ 5H₂O. The contentthereof is generally 1 wt. % or less.

Such metallic magnesium having an oxidized coating film with a thicknessof 1 μm or less can be produced by being formed into particles, forexample, cutting, milling, sieving or melting/spray, in an atmosphere ofan inert gas such as nitrogen.

The metallic magnesium is not critical with regard to its form and thelike, so far as an oxidized coating film has a thickness of 1 μm orless. Therefore metallic magnesium having any particle form, forexample, metallic magnesium having a granular, ribbon-shaped or powderyform, may be used. However, in order to ensure homogeneous reaction,particles with an average diameter of 1 cm or less are preferably used.When producing the particles with an average diameter of 1 cm or less,metallic magnesium may be subjected to processing such as cutting,milling, sieving and melting/spray preferably in an atmosphere of aninert gas such as nitrogen.

An alcohol, a halogen and a halogen-containing compound are the same asthose explained in the magnesium compound (a1) and their explanation isthus omitted.

In order to produce the magnesium compound (a4), metallic magnesiumsatisfying the above requirements, an alcohol, a halogen and/orhalogen-containing compound are reacted in the same manner as in themagnesium compound (a1).

The magnesium compound (a4) of the invention can be used as a supportfor a solid catalyst component without operations such as milling orclassification for a narrow particle distribution like the magnesiumcompound (a1). The magnesium compound (a4) is nearly spherical and has asharp particle size distribution. The particle thereof has a smallvariability of sphericity.

The magnesium compound (a4) generally has a particle size distributionindex (P′) represented by the above formula (IV) of less than 3.4,preferably less than 3.2.

The magnesium compound (a4) generally has a sphericity (S′) representedby the above formula (III) of less than 2.00, preferably 1.50.

Such a magnesium compound (a4) with a particle size distribution index(P′) of less than 3.4 and a sphericity (S′) of less than 2.00 ispreferred in view of catalyst activity and morphology of polymerparticles. Using the above metallic magnesium can produce such amagnesium compound (a4).

The magnesium compound (a4) may be used solely or two or more thereofprepared by different methods may be used in combination.

Such a magnesium compound (a4) is solid and substantially made of amagnesium alkoxide. Examples of the magnesium alkoxide are the same asthose of the magnesium compound (a1).

(b4) Titanium Compound

The titanium compound (b4) is as explained with regard to the titaniumcompound (b1) for use in the solid catalyst component [A1], so that itsexplanation is omitted.

(c4) Hologenated Compound

The hologenated compound (c4) is as explained with regard to thetitanium compound (c1) for use in the solid catalyst component [A1], sothat its explanation is omitted.

(d4) Electron-donating Compound

The electron-donating compound (d4) is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

[B] Organic Aluminum Compound

Although not specially limited, the organic aluminum compound [B] can bepreferably selected from an organic aluminum compound having an alkylgroup, a halogen atom, a hydrogen atom and an alkoxy group, aluminoxane,or a mixture of these. Specific examples thereof includetrialkylaluminum compounds such as trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum and trioctylaluminum;dialkylaluminum monochlorides such as diethylaluminum monochloride,diisopropylaluminum monochloride, diisobutylaluminum monochloride anddioctylaluminum monochloride; alkylaluminum sesquihalides such asethylaluminum sesquichloride; and linear aluminoxanes such asmethylaluminoxane. Of these organic aluminum compounds, trialkylaluminumhaving a lower alkyl group having 1 to 5 carbon atoms is preferred, andtrimethylaluminum, triethylaluminum, tripropylaluminum andtriisobutylaluminum are particularly preferred. These organic aluminumcompounds [B] may be used solely, or two or more thereof may be used incombination.

[C] Electron-donating Compound

If necessary, an electron-donating compound [C] is used for a catalystfor olefin polymerization. The electron-donating compound [C] ispreferably used since it may improve the stereoregularity of olefinpolymer. The electron-donating compound [C] can be selected from anorganosilicon compound having an alkoxy group, a nitrogen-containingcompound, a phosphorus-containing compound or an oxygen-containingcompound. Of these, it is particularly preferred to use an organosiliconcompound having an alkoxy group.

Specific examples of the organosilicon compound having an alkoxy groupinclude trimethylmethoxysilane, trimethylethoxysilane,triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, ethylisopropyldimethoxysilane,propylisopropyldimethoxysilane, diisopropyldimethoxysilane,diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane,di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane,t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane,t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane,t-butylisobutyldimethoxysilane, t-butyl(s-butyl)dimethoxysilane,t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane,t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane,t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane,t-butyl(3,3,3-trifluromethylpropyl)dimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane,cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane,cyclopentylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane,dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane,bis(2-methylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,α-naphthyl-1,1,2-trimethylpropyldimethoxysilane,n-tetradecanyl-1,1,2-trimethylpropyldimethoxysilane,1,1,2-trimethylpropylmethyldimethoxysilane,1,1,2-trimethylpropylethyldimethoxysilane,1,1,2-trimethylpropylisopropyldimethoxysilane,1,1,2-trimethylpropylcyclopentyldimethoxysilane,1,1,2-trimethylpropylcyclohexyldimethoxysilane,1,1,2-trimethylpropylmyristyldimethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,propyltrimethoxysilane, isopropyltrimethoxysilane,butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane,t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane,isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornenetrimethoxysilane, indenyl trimethoxysilane,2-methylcyclopentyl trimethoxysilane, ethyltriisopropoxysilane,methylcyclopentyl(t-butoxy)dimethoxysilane,isopropyl(t-butoxy)dimethoxysilane, t-butyl(t-butoxy)dimethoxysilane,(isobutoxy)dimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane,chlorotriethoxysilane, γ-chloropropyltrimethoxysilane,γ-aminopropyltriethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane,1,1,2-trimethylpropylisopropoxydimethoxysilane,1,1,2-trimethylpropyl(t-butoxy)dimethoxysilane, tetramethoxysilane,tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethylsilicate, butyl silicate, trimethylphenoxysilane,methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane,vinyltrisacetoxysilane and dimethyltetraethoxydisiloxane and the like.Of these, dicyclopentyldimethoxysilane,cyclohexylisobutyldimethoxysilane and cyclohexylmethyldimethoxysilaneare preferred.

Further, the above organosilicon compound also includes a compoundobtained by reacting a silicon compound having no Si—O—C bond with anorganic compound having an O—C bond in advance or by reacting thesecompounds during the polymerization of an α-olefin. Specifically, acompound obtained by reacting silicon tetrachloride and an alcohol isincluded.

Specific examples of the nitrogen-containing compound include2,6-substituted piperidines such as 2,6-diisopropylpiperidine,2,6-diisopropyl-4-methylpiperidine andN-methyl-2,2,6,6-tetramethylpiperidine; 2,5-substituted azolidines suchas 2,5-diisopropylazolidine and N-methyl-2,2,5,5-tetramethylazolidine;substituted methylenediamines such asN,N,N′,N′-tetramethylmethylenediamine andN,N,N′,N′-tetraethylmethylenediamine; and substituted imidazolidinessuch as 1,3-dibenzylimidazolidine and1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound includephosphorous acid esters such as triethyl phosphite, tri-n-propylphosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutylphosphite, diethyl-n-butyl phosphite and diethylphenyl phosphite.

Specific examples of the oxygen-containing compound include2,5-substituted tetrahydrofurans such as2,2,5,5-tetramethyltetrahydrofuran and2,2,5,5-tetraethyltetrahydrofuran; and dimethoxymethane derivatives suchas 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene,9,9-dimethoxyfluorene and diphenyldimethoxymethane.

These electron-donating compounds [C] may be used solely, or two or morethereof may be used in combination.

2. Method of Preparation of Solid Catalyst Component

As a method of preparing the solid catalyst component [A1] to [A4],there is exemplified a method in which the above magnesium compound (a1)to (a4) and the titanium compound (b1) to (b4), if necessary, and thehologenated compound (c1) to (c4) and/or the electron-donating compound(d1) to (d4) are brought into contact and react with each other, andpreferably the reaction mixture is thereafter brought into contact andreacts with the titanium compound (b1) to (b4) again (at least once).When the titanium compound (b1) to (b4) is brought into contact twice ormore, the titanium compound (b1) to (b4) can be sufficiently supportedon the magnesium compound (a1) to (a4) as a support of catalyst. Theorder of other contacts is not critical.

Further, these components may be brought into contact in the presence ofan inert solvent such as a hydrocarbon, or each component may be dilutedwith an inert solvent such as a hydrocarbon before they are brought intocontact. Examples of the above inert solvent include aliphatichydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane,n-octane and isooctane, aromatic hydrocarbons such as benzene, toluene,and xylene, or mixtures thereof. Of these, an aliphatic hydrocarbon ispreferred.

The amount of the titanium compound (b1) to (b4) per mole of magnesiumof the magnesium compound (a1) to (a4) is generally 0.5 to 100 moles,preferably 1 to 50 moles. If the amount is less than 0.5 mole, thepolymerization activity per titanium may decrease. On the other hand, ifit exceeds 100 moles, the polymerization activity per solid catalystcomponent may decrease.

When the hologenated compound (c1) to (c4) is used, the amount thereofper mole of magnesium of the magnesium compound (a1) to (a4) isgenerally 0.005 to 100 moles. If the amount is less than 0.005 mole, thepolymerization activity per titanium or the stereoregularity of polymermay decrease. On the other hand, if it exceeds 100 moles, thepolymerization activity per solid catalyst component may decrease.

Further, when the electron-donating compound (d1) to (d4) is used, theamount thereof per mole of magnesium of the magnesium compound (a1) to(a4) is generally 0.01 to 10 mol, preferably 0.05 to 0.15 mol. If theamount is less than 0.01 mole, the stereoregularity of polymer maydecrease. On the other hand, if it exceeds 10 moles, the polymerizationactivity per titanium may decrease.

These compounds are brought into contact generally in a temperaturerange of −20 to 200° C., preferably 20 to 150° C. Further, the contacttime is generally 1 minute to 24 hours, preferably 10 minutes to 6hours. When the contact reaction is carried out at the above temperatureand/or for the above time, the polymerization activity can be high andan olefin polymer can be obtained in an excellent form. Differingdepending upon a type of a solvent when it is used and a contacttemperature, etc., the pressure for the contact is generally in therange of 0 to 5 MPa, preferably 0 to 1 MPa. During the contactingprocedures, preferably, they are stirred in view of the uniformity andefficiency of the contact. These contact conditions are also applicableto the contact reaction that is carried out for the second time or morewith regard to the titanium compound (b1) to (b4).

When a solvent is used in the contact procedure of the titanium compound(b1) to (b4), the amount of the solvent per mole of the titaniumcompound (b1) to (b4) is generally 5,000 milliliters or less, preferably10 to 1,000 milliliters. When the ratio is outside the above range, theuniformity or efficiency of the contact may be degraded.

Further, a reaction product, which is from the first contact reaction ofthe compounds, is washed with an inert solvent, generally at atemperature of 90 to 150° C., preferably 120 to 140° C. When the washingtemperature is outside the above range, the catalyst activity or thestereoregularity may not be improved. The inert solvent can be selectedfrom the already explained aliphatic hydrocarbons and aromatichydrocarbons.

Although not especially limited with regard to the washing temperatureafter the contact reaction which is carried out for the second time ormore with the titanium compound (b1) to (b4), the washing is carried outwith an inert solvent, generally at a temperature of 90 to 150° C.,preferably 120 to 140° C., in view of stereoregularity.

Although not especially limited, the washing method is preferablyselected from a decantation or filtering method. Although the amount ofthe inert solvent, the washing time period and the number of times ofthe washing are not critical, the washing is carried out generally witha solvent in an amount, per mole of the magnesium compound (a1) to (a4),of 100 to 100,000 milliliters, preferably 1,000 to 50,000 milliliters,generally for 1 minute to 24 hours, preferably 10 minutes to 6 hours.When the above ratio is outside the above range, the washing may beincomplete.

While the pressure in the above case differs depending upon the type ofthe solvent, the washing temperature, and the like, the pressure isgenerally in the range of 0 to 5 MPa, preferably 0 to 1 MPa. For theuniformity of the washing and the washing efficiency, it is preferred tostir the reaction mixture during the washing. The thus-obtained solidcatalyst component [A1] to [A4] can be stored in a dry state or in aninert solvent such as a hydrocarbon.

3. Process for Producing Olefin Polymer

Although the amount of each component of the catalyst for olefinpolymerization is not especially limited, provided by the invention,each of the solid catalyst components [A1] to [A4] is used in such anamount that the titanium atom amount per liter of a reaction volume isgenerally in the range of 0.00005 to 1 mmol.

The organic aluminum compound [B] is used in such an amount that thealuminum/titanium (atomic ratio) is generally in the range of 1 to1,000, preferably 10 to 1,000. When the above atomic ratio is outsidethe above range, the catalyst activity is sometimes insufficient.

Further, the electron-donating compound [C] is used in such an amountthat the [C]/[B] (molar ratio) is generally in the range of 0.001 to5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0. When the abovemolar ratio is outside the above range, the sufficient catalyst activityand the stereoregularity sometimes cannot be obtained. When apreliminary polymerization is carried out, however, the amount of theelectron-donating compound [C] can be further decreased.

The olefin for use in the invention is preferably an—olefin of thefollowing general formula (VI).R¹—CH═CH₂  VI

In the above general formula (VI), R¹ is a hydrogen atom or ahydrocarbon group, and the hydrocarbon group may be saturated orunsaturated, may be linear or branched, or may be cyclic. Specificexamples of the olefin include ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene,4-methyl-1-pentene, vinylcyclohexane, butadiene, isoprene, piperylene,and the like. These olefins may be used solely, or two or more olefinsthereof may be used in combination. Of the above olefins, ethylene andpropylene are particularly preferred.

In the polymerization of an olefin in the invention, the preliminarypolymerization of an olefin may be carried out as required before theregular polymerization thereof in view of the polymerization activityand the stereoregularity and power form of an olefin polymer. In thiscase, the preliminary polymerization of an olefin is carried out in thepresence of a catalyst that is a mixture of predetermined amounts of thesolid catalyst component [A1] to [A4], the organic aluminum compound [B]and optionally the electron-donating compound [C] generally in thetemperature range of 0 to 100° C. under a pressure of atmosphericpressure to approximately 5 MPa, and then the regular polymerization ofthe olefin is carried out in the presence of the catalyst and thepreliminary polymerization product. The polymerization activity and theparticle properties of a polymer can be improved by carrying out thepreliminary polymerization.

Although the polymerization type of the regular polymerization is notespecially limited, any one of solution polymerization, slurrypolymerization, gaseous phase polymerization, bulk polymerization, etc.,can be employed. Further, any one of a batch polymerization and acontinuous polymerization can be employed, and there can be employedtwo-step polymerization or multi-step polymerization that is carried outunder different conditions.

Although the reaction condition is not especially limited, thepolymerization pressure therefor is generally selected from the range ofatmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and thepolymerization temperature is generally selected from the range of 0 to200° C., preferably 30 to 100° C., as required in view of polymerizationactivity. Although differing depending upon olefins and thepolymerization temperature, the polymerization time period is generally5 minutes to 20 hours, preferably approximately 10 minutes to 10 hours.

The molecular weight of an olefin polymer can be adjusted by adding achain transfer agent, preferably, hydrogen. Further, an inert gas suchas nitrogen may be present. For the catalyst components of theinvention, the solid catalyst component [A1] to [A4], the organicaluminum compound [B] and the electron-donating compound [C] may bemixed in predetermined amounts, and immediately thereafter, followed bythe introduction of an olefin for polymerization. Alternatively, theabove mixture may be aged for approximately 0.2 to 3 hours after thecontact, and then followed by the introduction of an olefin forpolymerization. Further, the above catalyst component may be suspendedin an inert solvent, an olefin, or the like and fed. In the invention,the post treatment after the polymerization can be carried out accordingto a conventional method. That is, in a gaseous phase polymerizationmethod, a nitrogen current may be allowed to pass through particles of apolymer powder introduced out of a polymerizer after the polymerization,for removing an olefin contained therein. Further, a polymer may bepelletized with an extruder as required, and in this case, a smallamount of water, an alcohol or the like may be added for deactivatingthe catalyst completely. In a bulk polymerization method, a polymer thatis withdrawn from a polymerizer after the polymerization can bepelletized after a monomer is completely separated from the polymer.

EXAMPLES

The invention will be explained with reference to Example hereinafter,while the invention shall not be limited to the following Examples. Thesphericity (S), particle size distribution index (P), average particlesize (D₅₀) and thickness of oxidized coating film of metallic magnesium;the sphericity (S′) and particle size distribution index (P′) ofmagnesium compounds; the sphericity (S″) and particle size distributionindex (P″) of polymer powders; and the stereoregularity [mmmm] ofpolymers were determined as follows.

-   (1) Sphericity (S) of metallic magnesium: Metallic magnesium was    photographed 40 times with a optical imcroscope (OLYMPUS Co., Ltd.,    BHS-751P). The photograph was subjected to image processing with an    image analyzer (Nexsus Co., Ltd.). In the processing, particles less    than 20 pixels (1 pixel: 0.4 μm×10.4 μm) were removed and the about    300 remaining particles were analyzed. The maximum diameter L₁ of    projection views of the particles, and the diameter L₂ of the circle    having the same area as that of projection view with the diameter L₁    were determined. Then a sphericity was calculated using the above    formula (I).-   (2) Particle size distribution index (P) of metallic magnesium: A    particle size distribution measured with sieves was plotted on a    logarithmic-normal probability paper, and a 50% particle size was    used as an average particle size (D₅₀). Further, a 90% particle size    (D₉₀) and a 10% particle size (D₁₀) were determined and then a    particle size distribution index was calculated using the above    formula (II).-   (3) Average particle size (D₅₀) of metallic magnesium: A particle    size distribution measured with sieves was plotted on a    logarithmic-normal probability paper, and a 50% particle size was    used as an average particle size (D₅₀).-   (4) Thickness of oxidized coating film of metallic magnesium:    Analysis was carried out with an ESCA (Electron Spectroscopy for    Chemical Analysis). Specifically metallic magnesium was subjected to    Ar ion etching and a layer from the uppermost surface to the depth    of 3 μm was analyzed. The existence of an oxidized coating film was    confirmed by using standard reagents (MgCO₃, Mg(OH)₂, MgSO₄, MgO,    MgSO₄ 7H₂O and (MgCO₃)₄ Mg(OH)₂ 5H₂O).-   (5) Sphericity (S′) of magnesium compound: A magnesium compound was    dried and then photographed 300 times (150 times in Examples 15    to 18) with a scanning electron microscope (JEOL Ltd., JSM-25SIII)    at an accelerating voltage of 5 KV to obtain a negative. Next the    negative was image-processed by a transmission method. In the image    processing, particles less than 20 pixels (1 pixel: 0.695 μm×0.695    μm (1.389 μm×1.389 μm in Examples 15 to 18)) were removed and the    about 2,000 remaining particles were analyzed with an image analyzer    (Nexsus Co., Ltd.). The maximum diameter L₃ of projection views of    the particles, and the diameter L₄ of the circle having the same    area as that of projection view with the diameter L₃ were    determined. Then a sphericity was calculated using the above formula    (III).-   (6) Particle size distribution index (P′) of magnesium compound: The    particle size of a magnesium compound was measured by a light    transmission method while the magnesium compound was suspended in a    hydrocarbon. The particle size distribution measured was plotted on    a logarithmic-normal probability paper, and a 50% particle size was    used as an average particle size (D₅₀). Further, a 90% particle size    (D₉₀) and a 10% particle size (D₁₀) were determined and then the    particle size distribution index was calculated using the above    formula (IV).-   (7) Sphericity (S″) of polymer powder: In Examples 1 to 4 and    Comparative Examples 1 to 3, the sphericity (S″) was measured in the    same manner as the sphericity (S′) of a magnesium compound.

In Examples 5 to 14 and Comparative Examples 4 to 12, the sphericity(S″) was measured in the same manner as the sphericity (S′) of amagnesium compound except that the following. The polyolefin powder wasphotographed 40 times with a optical imcroscope (OLYMPUS Co., Ltd.,BHS-751P), and the photograph was subjected to image processing. In theprocessing, one pixel was 10.4 μm×10.4 μm and about 300 particles wereanalyzed.

In Examples 15 to 18 and Comparative Examples 13 to 15, the sphericity(S″) was measured in the same manner as the sphericity (S′) of amagnesium compound except that polyolefin powder was image-analyzed by adirect reflection method and one pixel was 0.0813 mm×0.0813 mm in theimage analysis processing.

-   (8) Particle size distribution index (P″) of polymer powder: The    particle size distribution index (P″) was measured in the same    manner as the particle size distribution index (P) of metallic    magnesium.-   (9) Stereoregularity of polymer [mmmm]: A polymer was dissolved in    1,2,4-trichlorobenzene, and the stereoregularity of the polymer was    quantitatively determined on the basis of signals of methyl group    measured with a ¹³C-NMR (JEOL Ltd., EX-400) at 130° C. by a proton    complete decoupling method.

The isotactic pentad fraction [mmmm] means the isotactic fraction inpentad units of a polypropylene molecule chain determined on the basisof ¹³C-NMR spectrum, proposed by A. Zambelli, et al., in Macromolecules,vol. 6, page 925 (1973).

Further, a method of determining assignment of peaks of ¹³C-NMR spectrumwas according to the assignment proposed by A. Zambelli, et al., inMacromolecules, vol. 8, page 687 (1975).

Example 1

(1) Preparation of Magnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was subjected to replacement of an atmosphere therein with nitrogen gas.The flask was charged with 122 g of ethanol (2.64 gram atoms), 0.8 g ofiodine (6.3 mg atoms) and 8 g of metallic magnesium (0.33 gram atoms)with a sphericity of 1.85, which had been produced by an atomizationmethod. The mixture was reacted with stirring (350 rpm) at 78° C. untilhydrogen was not generated from the system to give a magnesium compound(diethoxymagnesium). Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was subjected to replacement of an atmosphere therein with nitrogen gas,and then the flask was charged with 80 mL of dehydrated octane and 16 gof the magnesium compound (support) prepared in the above (1). Themixture was heated to 40° C. Thereto was added 2.4 mL (23 mmol) ofsilicon tetrachloride and stirred for 20 minutes, followed by adding 3.4mL (13 mmol) of di-n-butyl phthalate. The resultant solution was heatedto 80° C. and 77 mL (0.70 mol) of titanium tetrachloride was dropwiseadded using a dropping funnel. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a titanationprocedure. After sufficiently washing with dehydrated octane, 122 mL(1.11 mol) of titanium tetrachloride was added and the mixture wasstirred at an internal temperature of 125° C. for 2 hours to carry out asecond titanation procedure. Sufficient washing with dehydrated octanegave a solid catalyst component.

(3) Propylene Slurry Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 L, was fully dried and then subjected to replacement of anatmosphere therein with nitrogen. The autoclave was charged with 500 mLof dehydrated heptane. The autoclave was further charged with 2.0 mmolof triethylaluminum, 0.25 mmol of dicyclopentyldimethoxysilane and0.0025 mmol, as Ti atom, of the solid catalyst component prepared in theabove (2), and hydrogen was introduced up to 0.1 MPa. Then, whilepropylene was introduced, the autoclave was temperature-increased to 80°C. and pressure-increased to a total pressure of 0.8 MPa, followed bypolymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 L of methanolto deactivate the catalyst. The product was separated by filtration andvacuum-dried to give a polypropylene. Table 1 shows the results.

Example 2

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 1(1)except that the amount of iodine was changed to 0.24 g (1.9 mg atoms),the reaction temperature was changed to 50° C. and the stirring speedwas changed to 525 rpm. Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

Example 3

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 1(1)except that the iodine was replaced with 0.30 g of anhydrous magnesiumchloride (6.3 mg atoms) in Example 1(1). Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

Example 4

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 1(1)except that metallic magnesium with a sphericity of 2.93 (prepared by acutting and ball mill method) was used. Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

Comparative Example 1

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 1(1)except that metallic magnesium with a sphericity of 5.20 (prepared by acutting method) was used. Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

Comparative Example 2

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 1(1)except that metallic magnesium with a sphericity of 5.80 (prepared by acutting method) was used and the reaction temperature was changed to 60°C. Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

Comparative Example 3

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 3(1)except that metallic magnesium with a sphericity of 6.95 (prepared by acutting method) was used. Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 1(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 1 shows the results.

TABLE 1 Com. Com. Com. Item Unit Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 2 Ex.3 Support Sphericity of Metallic Mg (S) 1.85 1.85 1.85 2.93 5.20 5.806.95 Initiator I₂ I₂ MgCl₂ I₂ I₂ I₂ MgCl₂ Halogen Comp./Mg (gram atom0.019 0.0057 0.019 0.019 0.019 0.019 0.019 molar) Reaction Temperature(° C.) 78 50 78 78 78 60 78 Number of Rotation (rpm) 350 525 350 350 350350 350 Average Particle Size (D₅₀) (μm) 68 34 69 67 76 62 80 Sphericity(S′) 1.23 1.21 1.25 1.28 1.34 1.38 1.85 PDDI (P′) 3.4 3.3 3.7 3.8 4.93.8 6.9 Polymer Polymerization Activity (kg/g-Cat) 16.8 24.9 16.3 15.813.1 15.0 12.7 Stereoregularity ([mmmm]) (mol %) 98.3 98.4 98.2 98.398.2 98.3 98.3 Average Particle Size (D₅₀) (μm) 1230 660 1210 1250 13201040 1380 Sphericity (S″) 1.23 1.20 1.24 1.29 1.36 1.40 1.90 PDDI (P″)3.5 3.4 3.8 3.8 5.2 3.9 7.2 Ex.: Example Com. Ex.: Comparative ExampleHalogen Comp.: Halogen and/or Halogen-containing Compound PDDI: Particlesize Distribution Index

Example 5

(1) Preparation of Magnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was replaced with nitrogen gas, and then 122 g (2.64 gram atoms) ofdehydrated ethanol, 0.8 g (6.3 mg atoms) of iodine and 8 g (0.33 gramatoms) of metallic magnesium with a particle size distribution index of1.4 (sieved after cutting and milling) were added therein. The mixturewas reacted at 78° C. while stirring (350 rpm) until hydrogen was nolonger generated from the system to obtain a magnesium compound(diethoxymagnesium). Table 2 shows the results.

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was subjected to replacement of an atmosphere therein with nitrogen gas,and then the flask was charged with 80 mL of dehydrated octane and 16 gof the magnesium compound (support) prepared in the above (1). Themixture was heated to 40° C. Thereto was added 2.4 mL (23 mmol) ofsilicon tetrachloride and stirred for 20 minutes, followed by adding 3.4mL (13 mmol) of di-n-butyl phthalate. The resultant solution was heatedto 80° C. and 77 mL (0.70 mol) of titanium tetrachloride was dropwiseadded using a dropping funnel. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a titanationprocedure. After sufficiently washing with dehydrated octane, 122 mL(1.11 mol) of titanium tetrachloride was added and the mixture wasstirred at an internal temperature of 125° C. for 2 hours to carry out asecond titanation procedure. Sufficient washing with dehydrated octanegave a solid catalyst component.

(3) Propylene Slurry Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 L, was fully dried and then subjected to replacement of anatmosphere therein with nitrogen. The autoclave was charged with 500 mLof dehydrated heptane. The autoclave was further charged with 2.0 mmolof triethylaluminum, 0.25 mmol of dicyclopentyldimethoxysilane and0.0025 mmol, as Ti atom, of the solid catalyst component prepared in theabove (2), and hydrogen was introduced up to 0.1 MPa. Then, whilepropylene was introduced, the autoclave was temperature-increased to 80°C. and pressure-increased to a total pressure of 0.8 MPa, followed bypolymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 L of methanolto deactivate the catalyst. The product was separated by filtration andvacuum-dried to give a polypropylene. Table 2 shows the results.

Example 6

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that the amount of iodine was changed to 0.24 g (1.9 mg atoms),the reaction temperature was changed to 50° C. and the number ofstirring was changed to 525 rpm. Table 2 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Example 7

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that the iodine was replaced with 0.30 g of anhydrous magnesiumchloride (6.3 mg atoms) in Example 5(1). Table 1 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Example 8

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that metallic magnesium with a particle size distribution indexof 3.0 (sieved after cutting and milling) was used. Table 2 shows theresults.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Example 9

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that metallic magnesium with a particle size distribution indexof 1.8 (sieved after cutting and milling) was used. Table 2 shows theresults.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Comparative Example 4

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that metallic magnesium with a particle size distribution indexof 4.9 (sieved after cutting and milling, and collected particles ofwidely varied diameters when sieved) was used. Table 2 shows theresults.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Comparative Example 5

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 5(1)except that metallic magnesium with a particle size distribution indexof 5.4 (sieved after cutting and milling, and collected particles ofwidely varied diameters when sieved) was used and the reactiontemperature was changed to 60° C. Table 2 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

Comparative Example 6

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 7(1)except that metallic magnesium with a particle size distribution indexof 7.0 (only cut and milled) was used. Table 2 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 5(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 2 shows the results.

TABLE 2 Com. Com. Item Unit Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Com. Ex. 4 Ex.5 Ex. 6 Support PDDI of Metallic Mg (P) 1.4 1.4 1.4 3.0 1.8 4.9 5.4 7.0Initiator I₂ I₂ MgCl₂ I₂ I₂ I₂ I₂ MgC1₂ Halogen Comp./Mg (gram atom0.019 0.0057 0.019 0.019 0.019 0.019 0.019 0.019 molar) ReactionTemperature (° C.) 78 50 78 78 78 78 60 78 Number of Rotation (rpm) 350525 350 350 350 350 350 350 Average Particle Size (D₅₀) (μm) 69 34 70 6869 74 61 77 PDDI (P′) 2.8 2.6 2.9 3.1 3.2 4.8 3.8 6.2 Sphericity (S′)1.30 1.28 1.31 1.32 1.30 1.36 1.35 1.63 Polymer Polymerization Activity(kg/g-Cat) 16.4 23.9 15.5 15.7 16.4 13.8 15.4 13.2 Stereoregularity([mmmm]) (mol %) 98.3 98.4 98.2 98.3 98.3 98.2 98.3 98.3 AverageParticle Size (D₅₀) (μm) 1,240 650 1,190 1,220 1,240 1,300 1,030 1,340PDDI (P″) 2.9 2.7 3.0 3.2 3.4 5.0 3.9 6.4 Sphericity (S″) 1.30 1.28 1.301.33 1.30 1.38 1.36 1.65 Ex.: Example Com. Ex.: Comparative ExampleHalogen Comp.: Halogen and/or Halogen-containing Compound PDDI: Particlesize Distribution Index

Example 10

(1) Preparation of Magnesium Compound

A three-necked flask, which has a stirrer with four baffles (maxblendblade, blade diameter (d)=0.09 m) and has an internal volume of 5 L, wasreplaced with nitrogen gas. The flask was charged with 2,274 g (49 gramatoms) of dehydrated ethanol, 12 g (95 mg atoms) of iodine and 120 g(4.9 gram atoms) of metallic magnesium with an average particle size of400 μm (cut and milled product) (ethanol/metallic magnesium (ROH/Mg)(molar ratio)=10). The mixture was reacted at 78° C. while stirring(number of stirring (n)=250 (number of revolution per minute)(hereinafter referred to as “rpm”), n³d²=1.27×10⁵) until hydrogen was nolonger generated from the system to obtain a magnesium compound(diethoxymagnesium). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was subjected to replacement of an atmosphere therein with nitrogen gas,and then the flask was charged with 80 mL of dehydrated octane and 16 gof the magnesium compound (support) prepared in the above (1). Themixture was heated to 40° C. Thereto was added 2.4 mL (23 mmol) ofsilicon tetrachloride and stirred for 20 minutes, followed by adding 3.4mL (13 mmol) of di-n-butyl phthalate. The resultant solution was heatedto 80° C. and 77 mL (0.70 mol) of titanium tetrachloride was dropwiseadded using a dropping funnel. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a titanationprocedure. After sufficiently washing with dehydrated octane, 122 mL(1.11 mol) of titanium tetrachloride was added and the mixture wasstirred at an internal temperature of 125° C. for 2 hours to carry out asecond titanation procedure. Sufficient washing with dehydrated octanegave a solid catalyst component.

(3) Propylene Slurry Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 L, was fully dried and then subjected to replacement of anatmosphere therein with nitrogen. The autoclave was charged with 500 mLof dehydrated heptane. The autoclave was further charged with 2.0 mmolof triethylaluminum, 0.25 mmol of dicyclopentyldimethoxysilane and0.0025 mmol, as Ti atom, of the solid catalyst component prepared in theabove (2), and hydrogen was introduced up to 0.1 MPa. Then, whilepropylene was introduced, the autoclave was temperature-increased to 80°C. and pressure-increased to a total pressure of 0.8 MPa, followed bypolymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 L of methanolto deactivate the catalyst. The product was separated by filtration andvacuum-dried to give a polypropylene. Table 3 shows the results.

Example 11

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 10(1)except that the amount of iodine was changed to 3.6 g (28 mg atoms), thereaction temperature was changed to 50° C. and the number of stirring(n) was changed to 375 rpm (n³d²=4.27×10⁵). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Example 12

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 10(1)except that the iodine was replaced with 1.5 g (31 mg atoms) ofanhydrous magnesium chloride and 40 g (1.6 g atoms) of metallicmagnesium (ROH/Mg=30) was used. Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Example 13

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 10(1)except that metallic magnesium with an average particle size (D₅₀) of 75μm (cut and milled product) was used, ethanol/metallic magnesium (molarratio) was changed to 8 and the number of stirring (n) was changed to150 rpm (n³d²=2.73×10⁴). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Example 14

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 13(1)except that metallic magnesium with an average particle size (D₅₀) of1,800 μm (cut and milled product) was used and the number of stirring(n) was 400 rpm (n³d²=5.18×10⁵). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 7

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 13(1)except that metallic magnesium with an average particle size (D₅₀) of2,400 μm (cutting and milling product) was used and the number ofstirring (n) was changed to 250 rpm (n³d²=1.27×10⁵). Table 3 shows theresults.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 8

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 11(1)except that metallic magnesium with an average particle size (D₅₀) of 40μm (cut and milled product) and the amount of iodine was changed to 3.6g (28 mg atoms) and the number of stirring (n) was changed to 200 rpm(n³d²=6.48×10⁴). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 9

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 10(1)except that ethanol/metallic magnesium (molar ratio) was changed to 50.Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 10

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 10(1)except that ethanol/metallic magnesium (molar ratio) was changed to 3.Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 11

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 13(1)except that metallic magnesium with an average particle size (D₅₀) of600 μm (cut and milled product) was used and the number of stirring (n)was changed to 60 rpm (n³d²=1.75×10³). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Comparative Example 12

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 13(1)except that metallic magnesium with an average particle size (D₅₀) of200 μm (cut and milled product) was used and the number of stirring (n)was changed to 800 rpm (n³d²=4.15×10⁶). Table 3 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 10(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

TABLE 3 Item Unit Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 M- Average Particle(μm) 400 400 400 75 1,800 Mg Size (D₅₀) Support Initiator I₂ I₂ MgCl₂ I₂I₂ Halogen Comp./Mg (gram atom 0.019 0.0057 0.019 0.019 0.019 molar)ROH/Mg (molar 10 10 30 8 8 ratio) Reaction (° C.) 78 50 78 78 78temperature Number of Rotation (rpm) 250 375 250 150 400 (n) Diameter of(m) 0.09 0.09 0.09 0.09 0.09 Stirring Blade (d) Stirring Condition1.27E+05 4.27E+05 1.27E+05 2.73E+04 5.18E+05 (n³d²) Average Particle(μm) 72 35 77 34 54 Size (D₅₀) PDDI (P) 3.0 2.9 3.2 3.1 3.2 Sphericity(S) 1.24 1.23 1.26 1.27 1.26 Polymer Polymerization (kg/g-Cat) 15.7 23.814.6 16.4 16.1 Activity Stereoregularity (mol %) 98.4 98.4 98.3 98.398.4 ([mmmm]) Average Particle (μm) 1,310 650 1,330 580 1,040 Size (D₅₀)PDDI (P′) 3.1 3.0 3.3 3.2 3.3 Sphericity (S′) 1.24 1.23 1.26 1.28 1.27Com. Com. Com. Com. Com. Com. Item Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 EX.12 M- Average Particle 2,400 40 400 400 600 200 Mg Size (D₅₀) SupportInitiator I₂ I₂ I₂ I₂ I₂ I₂ Halogen Comp./Mg 0.019 0.0057 0.019 0.0190.019 0.019 ROH/Mg 8 10 50 3 8 8 Reaction 78 78 78 78 78 78 temperatureNumber of Rotation 250 200 250 250 60 800 (n) Diameter of 0.09 0.09 0.090.09 0.09 0.09 Stirring Blade (d) Stirring Condition 1.27E+05 6.48E+041.27E+05 1.27E+05 1.75E+03 4.15E+06 (n³d²) Average Particle 103 15 88 6477 17 Size (D₅₀) PDDI (P) 4.3 4.4 4.7 4.8 4.7 4.8 Sphericity (S) 1.481.73 1.63 1.65 1.98 1.78 Polymer Polymerization 13.2 12.9 12.7 11.9 12.512.2 Activity Stereoregularity 98.1 98.2 98.3 98.2 98.2 98.3 ([mmmm])Average Particle 1,800 330 1,690 1,220 1,340 360 Size (D₅₀) PDDI (P′)4.5 4.8 4.9 5.0 4.9 5.1 Sphericity (S′) 1.48 1.75 1.65 1.68 2.04 1.48Ex.: Example Com. Ex.: Comparative Example M-Mg: Metallic Mg HalogenComp.: Halogen and/or Halogen-containing Compound PDDI: Particle sizeDistribution Index

Example 15

(1) Preparation of Magnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was replaced with nitrogen gas. The flask was charged with 122 g (2.64gram atoms) of dehydrated ethanol, 0.8 g (6.3 mg atoms) of iodine and 8g (0.33 gram atoms) of metallic magnesium with an oxidized coating filmhaving a thickness of 0.05 μm (an average particle size of 400 μm,obtained by cut, milled and sieved under an atmosphere of nitrogen gas).The mixture was reacted at 78° C. while stirring (number of stirring(n)=350 rpm) until hydrogen was no longer generated from the system toobtain a magnesium compound (diethoxymagnesium). Table 4 shows theresults.

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5 L,was subjected to replacement of an atmosphere therein with nitrogen gas,and then the flask was charged with 80 mL of dehydrated octane and 16 gof the magnesium compound (support) prepared in the above (1). Themixture was heated to 40° C. Thereto was added 2.4 mL (23 mmol) ofsilicon tetrachloride and stirred for 20 minutes, followed by adding 3.4mL (13 mmol) of di-n-butyl phthalate. The resultant solution was heatedto 80° C. and 77 mL (0.70 mol) of titanium tetrachloride was dropwiseadded using a dropping funnel. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a titanationprocedure. After sufficiently washing with dehydrated octane, 122 mL(1.11 mol) of titanium tetrachloride was added and the mixture wasstirred at an internal temperature of 125° C. for 2 hours to carry out asecond titanation procedure. Sufficient washing with dehydrated octanegave a solid catalyst component.

(3) Propylene Slurry Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 L, was fully dried and then subjected to replacement of anatmosphere therein with nitrogen. The autoclave was charged with 500 mLof dehydrated heptane. The autoclave was further charged with 2.0 mmolof triethylaluminum, 0.25 mmol of dicyclopentyldimethoxysilane and0.0025 mmol, as Ti atom, of the solid catalyst component prepared in theabove (2), and hydrogen was introduced up to 0.1 MPa. Then, whilepropylene was introduced, the autoclave was temperature-increased to 80°C. and pressure-increased to a total pressure of 0.8 MPa, followed bypolymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 L of methanolto deactivate the catalyst. The product was separated by filtration andvacuum-dried to give a polypropylene. Table 4 shows the results.

Example 16

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 15(1)except that the amount of iodine was changed to 0.24 g (1.9 mg atoms),the reaction temperature was changed to 50° C. and the number ofstirring was changed to 525 rpm. Table 4 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 4 shows the results.

Example 17

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 15(1)except that the iodine was replaced with 0.30 g (6.3 mg atoms) ofanhydrous magnesium chloride in Example 15(1). Table 4 shows theresults.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 3 shows the results.

Example 18

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 15(1)except that metallic magnesium having an oxidized coating film with athickness of 0.5 μm (an average particle size of 400 μm, obtained bycut, milled and sieved under an atmosphere of nitrogen gas) was used.Table 4 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 4 shows the results.

Comparative Example 13

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 15(1)except that metallic magnesium having an oxidized coating film with athickness of 2 μm (an average particle size of 300 μm, obtained by cut,milled and sieved in air) was used. Table 4 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 4 shows the results.

Comparative Example 14

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 17(1)except that the same metallic magnesium as that in Comparative Example 1was used. Table 4 shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 4 shows the results.

Comparative Example 15

(1) Preparation of Magnesium Compound

A magnesium compound was obtained in the same manner as in Example 15(1)except that the same metallic magnesium as that in Comparative Example13 was used and the reaction temperature was changed to 60° C. Table 4shows the results.

(2) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example15(2) except that the magnesium compound prepared in the above (1) wasused.

(3) Propylene Slurry Polymerization

Propylene was polymerized in the same manner as in Example 15(3) exceptthat the solid catalyst component prepared in the above (2) was used.Table 4 shows the results.

TABLE 4 Com. Com. Com. Item Unit Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 13 Ex.14 Ex. 15 Support Thickness of Oxidized (μm) 0.05 0.05 0.05 0.5 2 2 2Film of Metallic Mg Initiator I₂ I₂ MgCl₂ I₂ I₂ MgCl₂ I₂ HalogenComp./Mg (gram atom 0.019 0.0057 0.019 0.019 0.019 0.019 0.019 molar)Reaction Temperature (° C.) 78 50 78 78 78 78 60 Number of Rotation(rpm) 350 525 350 350 350 350 350 Average Particle (μm) 68 35 69 70 7273 49 Size (D₅₀) PDDI (P) 3.0 2.9 3.0 3.2 4.7 4.9 3.8 Sphericity (S)1.30 1.28 1.32 1.31 1.50 1.53 1.40 Polymer Polymerization Activity(kg/g-Cat) 16.2 24.2 15.9 15.0 13.3 13.2 14.9 Stereoregularity (mol %)98.4 98.4 98.3 98.3 98.2 98.2 98.3 ([mmmm]) Average Particle (μm) 1,250650 1,200 1,220 1,250 1,280 1,080 Size (D₅₀) PDDI (P′) 3.1 2.9 3.1 3.34.6 4.8 3.942 Sphericity (S′) 1.29 1.28 1.32 1.31 1.52 1.55 1.64 Ex.:Example Com. Ex.: Comparative Example Halogen Comp.: Halogen and/orHalogen-containing Compound PDDI: Particle size Distribution Index

INDUSTRIAL UTILITY

The invention can provide a magnesium compound, a solid catalystcomponent for olefin polymerization, a catalyst for olefinpolymerization and a method for producing a polyolefin. A polyolefinwith a narrow particle size distribution and/or a nearly spherical formcan be obtained without reducing stereoregularity and catalystproperties such as polymerization activity by using the magnesiumcompound of the invention.

1. A method for producing a magnesium compound, comprising reactingmetallic magnesium having a sphericity (S) of less than 2.50, thesphericity (S) being represented by the following formula (I), analcohol, and a halogen and/or a halogen-containing compound containinghalogen atoms in an amount of 0.0001 gram atom or more relative to onegram atom of the metallic magnesium,S=(L ₁ /L ₂)³  (I) wherein L₁ represents a maximum diameter ofprojection views of metallic magnesium determined by imaging metallicmagnesium with a scanning electron microscope, and L₂ represents thediameter of a circle having an area equal to the area of the projectionview of metallic magnesium having said maximum diameter L₁; wherein themagnesium compound has a sphericity (S′) of less than 1.30, thesphericity (S′) being represented by the following formula (III),S′=(L ₃ /L ₄)³  (III) wherein L₃ represents a maximum diameter ofprojection views of the magnesium compound determined by imaging themagnesium compound with a scanning electron microscope, and L₄represents the diameter of a circle having an area equal to the area ofthe projection view of the magnesium compound having said maximumdiameter L₃.
 2. The method according to claim 1, wherein the halogen isiodine.
 3. The method according to claim 1, wherein thehalogen-containing compound is magnesium chloride.
 4. The methodaccording to claim 1, wherein the metallic magnesium, the alcohol andthe halogen and/or the halogen-containing compound are reacted at atemperature of from 30 to 90° C.